JP7824253B2 - Inverted container assembly and cleaning product including a viscous cleaning composition - Google Patents

Description

The present invention relates to a cleaning product comprising an inverted container assembly and a liquid hand dishwashing cleaning composition having a specific surfactant system to substantially reduce/prevent unwanted liquid leakage caused by temporary increases in liquid pressure (e.g., hydraulic hammer pressure) and/or to substantially improve the reduction/prevention of stringing of the liquid during dosing.

An inverted container is a container with an opening at the "bottom" for dispensing the liquid detergent contained therein. Typically, consumers squeeze the side of the inverted container to dispense the liquid detergent. The use of inverted containers to package consumer products is becoming more common, particularly in the field of liquid hand dishwashing products. For example, Method Products Inc.'s "Method Dish Soap" brand and retailer Lidl's "Geschirr Spul Mittel" brand detergent are packaged in inverted containers (see Figures 1a and 1b). Consumers prefer inverted containers because they are ergonomically easier to operate. For example, unlike traditional upright containers, inverted containers do not require consumers to continually twist their wrist to dispense the liquid detergent, which can be inconvenient or difficult, especially when using larger bottle sizes and/or for older consumers. Furthermore, inverted containers facilitate dispensing every last drop, which is more difficult with traditional upright containers that have an opening at the "top." The terms "bottom" and "top" should be interpreted according to the intended orientation of the container during storage, i.e., when not in use. For example, when the container is stored, an inverted container has an opening at the bottom, while an upright container has an opening at the top. A further advantage of inverted containers is that they positively impact physical stability and/or perfume longevity by minimizing the risk of perfume and/or solvent evaporation when left open. Inverted containers also prevent dispensed liquid detergent from mixing with external air when the container is rotated (which can ultimately lead to splashing during "air" dispense).

A particular challenge with inverted containers is leak prevention, especially when the inverted container does not include a closure lid. As used herein, the term "closure lid" means a physical closure (i.e., a solid member) that blocks the bottle outlet such that the consumer must physically remove/move the solid member to allow dispensed liquid to exit through the bottom opening. An example of a closure lid is a flip-top cap that is movable between a closed and an open position. Those skilled in the art will recognize other possible closure lids. It will be understood that the following items are not considered "closure lids": a one-way or two-way valve or a baffle located at the bottle outlet, or a strip applied to prevent leakage during transport and removed before first use.

The lack of a closing lid is preferred by consumers for its one-handed dispensing operation, as it eliminates the need to open and close the lid with the other hand, as well as requiring fewer steps, making the dispensing operation quicker. Liquid contained within an inverted container is prone to leakage during steady-state conditions (i.e., storage) and/or upon impact, particularly upon impact. For example, leakage may occur during storage when the inverted container is subjected to temperature changes, specifically increases (e.g., an inverted container placed next to a sunny window or near a stove top), which may lead to an increase in internal pressure and leakage. Specifically, "impact" refers to when the inverted container is handled, transported, dropped, or knocked over. As a result of the impact, temporary liquid pressure, also known as water hammer pressure, may build up inside the inverted container, causing leakage through the opening in the bottom.

Previous attempts to address the leakage problem have involved incorporating a resilient valve into the opening (see, e.g., WO 2004/02843 (Method Products)). However, it has been observed that even with a resilient valve, some leakage may still occur. Other attempts have incorporated a baffle over the resilient valve (see, e.g., JP 2007/176594 (Lion) and WO 2000/6038 (Aptar Group)), but have not fully addressed the issue of leakage upon impact, specifically with respect to inverted containers. Still other attempts have involved incorporating a flowable, viscous (at least 500 Pa·s) laundry composition inside a compressible inverted container with a lid that acts as a support base (see, e.g., WO 2009/156317 (Unilever)). None of these solutions adequately address the above issues.

This leakage problem is compounded by the fact that these commercially available liquid dishwashing cleaning compositions are relatively highly viscous (i.e., >3,000 mPa·s), which makes dispensing and especially dissolving the compositions more difficult and may limit formulators' use of techniques that make it difficult to achieve such high product viscosities. It has also been observed that these compositions tend to "string" when the consumer stops dispensing the liquid composition (i.e., stops applying force to the sides of the inverted container). "Stringing" is a phenomenon in which the liquid composition remains attached to the bottom opening of the inverted container, forming a "capillary" between the bottom opening and the external environment. As a result of stringing, a portion of the liquid composition is left behind around and within the bottom opening. This liquid composition tends to dry out and form a crust. If the crust accumulates, the opening will eventually become blocked. Alternatively, a stringy liquid composition may fall under the influence of gravity during storage, eventually damaging sensitive storage surfaces.

The surfactant systems in these commercially available liquid dishwashing cleaning compositions are believed to contribute to the compositions' high viscosity profile, causing the observed leakage and/or stringing. For example, Method Products' "Method Dish Soap" brand detergent contains an anionic-nonionic surfactant system, and retailer Lidl's "Geschirr Spul Mittel" brand detergent contains a highly viscous alkyl ethoxy sulfate anionic surfactant and a cocoamidopropyl betaine zwitterionic surfactant system in a ratio of greater than 8:1.

WO 2004/02843 JP 2007/176594 A WO 2000/6038 International Publication No. 2009/156317

Thus, there remains a need for improved cleaning products comprising an inverted container assembly and a liquid hand dishwashing cleaning composition contained therein. It is desirable that the specific surfactant system of the liquid composition help substantially reduce or prevent leakage of liquid when the inverted container is subjected to impact, particularly when dropped or tipped over. It is also desirable that the specific surfactant system of the liquid composition help substantially reduce or prevent steady-state leakage of liquid from the inverted container. There is also a need for improved cleaning products comprising an inverted container and a liquid composition having a specific surfactant system to substantially reduce or prevent stringing of the liquid composition, preferably during dispensing, and more preferably upon completion of dispensing. Preferably, this product formulation approach also allows for lower product viscosity to facilitate the product's dispensing and dissolution profile. Faster product dissolution also results in faster foam generation, signaling to the user that the product is ready to use. Applicant has discovered that some or all of the above-mentioned needs can be met, at least in part, through the improved cleaning products described herein below.

The present invention satisfies one or more of these needs based on the surprising discovery that cleaning products comprising an inverted container assembly and a cleaning composition having a surfactant system comprising an anionic surfactant and a first co-surfactant system in a ratio of 8:1 to 1:1 exhibit improved leakage and/or stringing prevention.

In one aspect, the present invention addresses these needs by providing a cleaning product that includes an inverted container assembly and a liquid dishwashing cleaning composition. The inverted container assembly includes an inverted container having a bottom surface with an opening and a top surface positioned away from the bottom surface. A liquid dispenser is attached, preferably removably attached, to the bottom surface of the inverted container. The liquid dispenser controls the dispensing of the cleaning composition from the bottom of the inverted container. The cleaning composition comprises from 1% to 60% by weight of surfactants comprising: i) an anionic surfactant, preferably selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, and mixtures thereof, where the alkyl alkoxy sulfate is preferably an alkyl ethoxy sulfate; and ii) a first co-surfactant system, selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, where the first co-surfactant system is preferably an amphoteric surfactant, preferably an amine oxide surfactant, wherein the composition comprises the anionic surfactant and the first co-surfactant system in a weight ratio of from 8:1 to 1:1, preferably from 4:1 to 2:1, and more preferably from 3.5:1 to 2.5:1. This particular surfactant system enables the cleaning composition to have a lower shear viscosity, which functions effectively to substantially reduce or prevent leakage, particularly during impaction, and/or to prevent the possibility of stringing of the liquid after dispensing is complete.

In another aspect, the present invention relates to a method of cleaning dishes using a cleaning product according to the claims, the method comprising squeezing an inverted container to dispense the cleaning composition through an opening in the bottom.

In yet another aspect, the present invention relates to the use of a cleaning product according to the claims to substantially reduce or prevent leakage of a cleaning composition from an inverted container, preferably when the inverted container is subjected to water hammer pressure.

In yet another aspect, the present invention relates to the use of a cleaning product according to the claims to substantially reduce or prevent stringing of a cleaning composition, preferably upon completion of dispensing.

In yet another aspect, the present invention relates to a cleaning product comprising a liquid cleaning composition according to the present invention and an inverted container assembly comprising an inverted container and a liquid dispenser attached, preferably removably attached, to the inverted container as claimed. Preferably, the inverted container does not include a closure cap or seal.

One object of the present invention is to provide a cleaning product as described herein that is substantially improved in reducing and/or preventing leakage of the cleaning composition when the inverted container is subjected to impact, particularly when dropped or tipped over. Such improved cleaning products will also accommodate more rough handling or misuse of the inverted container.

Another object of the present invention is to provide a cleaning product as described herein that substantially reduces and/or prevents steady-state leakage of the cleaning composition. Advantageously, the cleaning composition will not leak unless a force is intentionally applied to the inverted container to dispense the liquid. This avoids messy liquid drying near the dispensing orifice, which can potentially prevent the liquid from being dispensed, or clutter in storage areas that can be left on sensitive surfaces and ultimately lead to surface damage.

It is a further object of the present invention to provide a cleaning product as described herein that substantially reduces and/or prevents liquid stringing after dispensing is complete, such that the cleaning composition does not dry and form a crust around and inside the opening in the bottom of the inverted container. Such an improved cleaning product would prevent dispensing problems by avoiding liquid mess and a crust of liquid drying around the liquid dispenser.

It is a further object of the present invention to provide cleaning products as described herein that allow for easy and accurate dispensing without the need to turn the container upside down. This is believed to contribute to a faster and more ergonomic dispensing experience (i.e., more comfortable, less stress on the wrist, less force required, etc.).

It is yet a further object of the present invention to provide a cleaning product as described herein that allows for the utilization of every last drop of liquid in an inverted container, thereby minimizing waste, which is an advantage of the present invention.

Another advantage of the present invention is that it allows for the use of larger sized inverted containers (e.g., >450 mL). The improved cleaning product is expected to allow for higher weight tolerances when used with larger inverted containers, thereby substantially reducing/preventing liquid spillage.

These and other features, aspects, and advantages of the present invention will become apparent to those skilled in the art from the following detailed description.

While this specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed the present invention will be better understood from the following description of the accompanying drawings, in which like numerals are used to designate like parts throughout.
1 shows "Method Dish Soap," a liquid dishwashing detergent manufactured by Method Products Inc. (as disclosed in WO 2004/02843) packaged in an inverted container. 1 shows "Geschirr Spul Mittel" liquid dishwashing detergent packaged in an inverted container from retailer Lidl. 1 shows a perspective view of a cleaning product according to one aspect of the present invention, the cleaning product comprising an inverted container assembly (10) comprising an inverted container (11) connected to a liquid dispenser (15) and a cleaning composition (100) contained therein. 1 shows a perspective view of a liquid dispenser (15) according to the present invention. 1 shows a perspective view of the body (16) of a liquid dispenser (15) according to the present invention. Figure 1 shows a plan view of the inside (20) of the valve (19) of a liquid dispenser (15) according to the present invention. FIG. 1 shows a perspective bottom view of the exterior (21) of the valve (19) of a liquid dispenser (15) according to the present invention. 4 shows a perspective view of the liquid dispenser (15) of FIG. 3 according to the present invention with a baffle (30). Figure 1 shows a perspective view of an anti-shock system (23) of a liquid dispenser (15) according to the present invention. Figure 1 shows a cross-sectional view of the anti-shock system (23) of a liquid dispenser (15) according to the present invention before "shock" and when the compressible material (110) is uncompressed. 1 shows the drop test apparatus from the leak resistance test method.

It is to be understood that the claims are not limited to the specific devices, apparatus, methods, conditions, or parameters described and/or illustrated herein, and that the terminology used herein is used by way of example only to describe particular aspects of the invention and is not intended to limit the invention as claimed.

As used herein, articles such as "a" and "an" used in the claims are understood to mean one or more of what is claimed or described.

As used herein, the terms "comprising," "having," "containing," and "including" all mean that other steps, ingredients, elements, etc. can be added that do not adversely affect the end result. Each of these terms encompasses the terms "consisting of" and "consisting essentially of." Unless otherwise specified, elements and/or equipment herein are believed to be widely available from numerous suppliers and sources worldwide.

As used herein, the term "compressibility" means the ability of a substance to reduce in volume under the influence of increased pressure, the reduction in volume being at least 1%, preferably at least 5%, and most preferably at least 10%.

As used herein, the term "consumer" is meant to include the person who uses the cleaning product as well as the customer who purchases the product.

As used herein, the term "water hammer" refers to the temporary increase in pressure that occurs when the liquid in the inverted container (11) is suddenly stopped or redirected (i.e., its momentum is changed), typically as a result of an impact to the inverted container (11). Water hammer may also be referred to as "impact force." If the water hammer force is not absorbed by the liquid dispenser (15), the force may (momentarily) open the valve, causing the liquid to leak out.

The terms "include," "includes," and "including" are meant to be non-limiting.

As used herein, the term "steady state" refers to the constant pressure characteristic of the liquid inside the inverted vessel (11) at rest.

Dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "1.2 cm" is intended to mean "approximately 1.2 cm."

It is understood that the test methods disclosed in the Test Methods section of this application must be used to determine the values of each of the parameters of Applicants' inventions described and claimed herein.

In all embodiments of the present invention, unless specifically stated otherwise, and as is clear from the context, all percentages are by weight of the total composition. Unless specifically stated otherwise, all ratios are by weight, and all measurements are made at 25°C unless otherwise specified.

Cleaning Product Applicants have surprisingly discovered that an improved cleaning product comprising an inverted container assembly (10) and a liquid dishwashing cleaning composition (100) provides substantially improved reduction/prevention of leakage and stringing of liquid. Essentially, the solution is to formulate the cleaning composition (100) with a specific surfactant system comprising an anionic surfactant and a first co-surfactant system, preferably an amphoteric surfactant, more preferably an amine oxide surfactant, wherein the anionic surfactant and the first co-surfactant system are present in a weight ratio of from 8:1 to 1:1, preferably from 4:1 to 2:1, more preferably from 3.5:1 to 2.5:1. Indeed, the inventors have found that this particular surfactant system allows the cleaning composition (100) to have a lower shear viscosity profile (i.e., ≦10,000 mPa·s), which substantially reduces/prevents leakage upon impact of the inverted container (11) and/or stringing of the cleaning composition (100) upon dispensing, preferably upon completion of dispensing. Without being bound by theory, it is believed that the particular surfactant system in the cleaning composition (100) herein affects the elastic properties of the liquid cleaning composition (100), allowing the composition to have high elasticity at low shear, thereby making the product less susceptible to leakage during storage or upon "water hammer" impact. The particular surfactant system also allows the composition to have low elasticity at high shear, thereby substantially reducing or preventing liquid stringing, preferably upon dispensing, more preferably upon completion of dispensing.

For ease of description, the cleaning product of the present invention will be described using terms such as upper/top, lower/bottom, and horizontal with reference to the positions shown in FIG. 2. With continued reference to FIG. 2, it will be understood that the cleaning product of the present invention comprises an inverted container assembly (10) and a liquid dishwashing cleaning composition (100) contained within the inverted container assembly (10). The inverted container assembly (10) comprises an inverted container (11) having a bottom surface (12) (not shown) and a top surface (13) positioned away from the bottom surface (12). The bottom surface (12) has an opening (14), and a liquid dispenser (15) is attached, preferably removably attached, to the bottom surface (12) of the inverted container (11) for controlling the amount of liquid dispensed from the bottom of the inverted container (11).

Cleaning Composition The cleaning composition (100) of the present invention comprises a specific surfactant system to improve leakage and/or stringing prevention while also allowing for a lower shear viscosity profile of the product. The composition comprises from 1% to 60%, preferably from 5% to 50%, more preferably from 8% to 45%, and most preferably from 15% to 40% by weight of the total composition of the surfactant system. The surfactant system comprises an anionic surfactant and a first co-surfactant in a weight ratio of from 8:1 to 1:1, preferably from 4:1 to 2:1, and more preferably from 3.5:1 to 2.5:1.

Preferably, the pH of the cleaning composition (100) is 5 to 12, more preferably 7.5 to 10, when measured at a 10% dilution in distilled water at 20°C. The pH of the composition can be adjusted using pH-adjusting ingredients known in the art.

The compositions of the present invention can be Newtonian or non-Newtonian fluids, but are preferably Newtonian fluids. Preferably, the compositions have a shear viscosity of 10 mPa·s to 10,000 mPa·s, preferably 100 mPa·s to 5,000 mPa·s, more preferably 300 mPa·s to 2,000 mPa·s, or most preferably 500 mPa·s to 1,500 mPa·s, or a combination thereof. Shear viscosity is measured according to the Shear Viscosity Test Method described herein.

The composition preferably has a density of 0.5 g/mL to 2 g/mL, more preferably 0.8 g/mL to 1.5 g/mL, and most preferably 1 g/mL to 1.2 g/mL.

The cleaning composition (100) of the present invention is particularly suitable for use as a hand dishwashing detergent. The composition is highly suitable for use in diluted form in a sink filled with water to wash dishes. The composition can also be used when dispensed directly onto soiled dishes or onto an optionally pre-wetted cleaning implement, preferably a sponge.

Anionic Surfactants Preferably, the surfactant system for the cleaning composition (100) of the present invention comprises 60% to 90%, preferably 65% to 85%, more preferably 70% to 80% by weight of the surfactant system of anionic surfactant. The anionic surfactant can be any anionic detersive surfactant, preferably selected from sulfate and/or sulfonate and/or sulfosuccinate anionic surfactants. Particularly preferred anionic surfactants are selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, and mixtures thereof. Preferred anionic surfactants are alkyl ethoxy sulfates or mixed alkyl sulfate-alkyl ethoxy sulfate anionic surfactant systems having a molar average degree of ethoxylation of less than 5, preferably less than 3, more preferably less than 2, and greater than 0.5.

Preferably, the alkyl ethoxy sulfate, or mixed alkyl sulfate-alkyl ethoxy sulfate, anionic surfactant has a weight average branching level of 5% to about 60%, preferably 10% to 50%, and more preferably 20% to 40%. This branching rate contributes to better dissolution and foam retention. It also contributes to the stability of the detergent at low temperatures. Preferably, the alkyl ethoxy sulfate anionic surfactant, or mixed alkyl sulfate-alkyl ethoxy sulfate anionic surfactant, has an average alkyl carbon chain length of 8 to 16, preferably 12 to 15, more preferably 12 to 14, and a weight average branching rate of preferably 25 to 45%. Detergents with this ratio exhibit good dissolution and foam performance. Even without control of the alkyl carbon chain length, the average degree of ethoxylation and average branching also help control the shear viscosity of the cleaning composition (100) without the need for excessive organic solvents.

When the alkyl ethoxylated sulfate anionic surfactant is a mixture, the average degree of alkoxylation is the molar average degree of alkoxylation of all components of the mixture (i.e., the molar average degree of alkoxylation). The calculation of the molar average degree of alkoxylation should also include the weight of sulfate anionic surfactant components that do not have alkoxylate groups.

Molar average degree of alkoxylation = (x1 x alkoxylation degree of surfactant 1 + x2 x alkoxylation degree of surfactant 2 + . . .) / (x1 + x2 + . . .)
where x1, x2, ... are the number of moles of each sulfate anionic surfactant in the mixture, and the degree of alkoxylation is the number of alkoxy groups in each sulfate anionic surfactant.

When the surfactant is branched, the preferred branching group is alkyl. Typically, the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, cyclic alkyl groups, and mixtures thereof. Single or multiple alkyl branches may be present in the hydrocarbyl backbone of the starting alcohol used to make the sulfate anionic surfactant used in the compositions of the present invention.

The branched sulfate anionic surfactant may be a single anionic surfactant or a mixture of anionic surfactants. In the case of a single surfactant, the percent branching refers to the weight percent of hydrocarbyl chains that are branched in the original alcohol from which the surfactant is derived.

For surfactant mixtures, the branching percentage is weight average and is defined according to the following formula:
Weight average of branching (%) = [(x1 ^* weight % of branched alcohol 1 in alcohol 1 + x2 ^* weight % of branched alcohol 2 in alcohol 2 + ...) / (x1 + x2 + ...)] ^* 100
(where x1 and x2 are the weights (grams) of each alcohol in the total alcohol mixture used as starting materials for the anionic surfactants for the detergents of the present invention.) The calculation of the weight average degree of branching should also include the weight of the anionic surfactant components that do not have branching groups.

Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, preferably sodium.

Suitable commercially available sulfates include Neodol alcohols from Shell, Lial-Isalchem and Safol® from Sasol, and natural alcohol-based surfactants from Procter & Gamble Chemicals. Suitable sulfonate surfactants for use herein include water-soluble salts of C8-C18 alkyl or hydroxyalkyl sulfonates; C11-C18 alkyl benzene sulfonates (LAS), modified alkyl benzene sulfonates (MLAS); methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS). These also include paraffin sulfonates, which may be monosulfonates and/or disulfonates obtained by sulfonating paraffins of 10 to 20 carbon atoms. Sulfonate surfactants also include alkyl glyceryl sulfonate surfactants.

First Co-surfactant The surfactant system of the composition of the present invention comprises a first co-surfactant. The composition preferably comprises from 0.1% to 20%, more preferably from 0.5% to 15%, especially from 2% to 10% of the first co-surfactant by weight of the cleaning composition (100). Preferably, the surfactant system for the cleaning composition (100) of the present invention comprises from 10% to 40%, preferably from 15% to 35%, more preferably from 20% to 30% of the first co-surfactant by weight of the surfactant system.

As used herein, the term "first co-surfactant" means a non-anionic surfactant present in the highest concentration of all co-surfactants co-formulated with an anionic surfactant. Preferably, the primary co-surfactant is selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

The composition of the present invention preferably contains an amine oxide as an amphoteric surfactant. Preferably, the amine oxide surfactant is selected from the group consisting of linear or branched alkylamine oxide surfactants, linear or branched alkylamidopropylamine oxide surfactants, and mixtures thereof, more preferably linear alkyldimethylamine oxide surfactants, even more preferably linear C10 alkyldimethylamine oxide surfactants, linear C12-C14 alkyldimethylamine oxide surfactants, and mixtures thereof, and most preferably linear C12-C14 alkyldimethylamine oxide surfactants.

Preferably, the amine oxide surfactant is an alkyl dimethyl amine oxide or alkyl amidopropyl dimethyl amine oxide, preferably an alkyl dimethyl amine oxide, particularly coco dimethyl amine oxide, and most preferably a C12-C14 alkyl dimethyl amine oxide.

Alternatively, the amine oxide surfactant is a mixture of amine oxides, including a low cut amine oxide and a mid cut amine oxide. The amine oxide of the composition of the present invention may also be
a) 10% to 45% by weight of the amine oxide of a low cut amine oxide of the formula R1R2R3AO, where R1 and R2 are independently selected from hydrogen, C1-C4 alkyl, or mixtures thereof, and R3 is selected from C10 alkyl or mixtures thereof;
b) 55% to 90% by weight of the amine oxide of a mid-cut amine oxide of the formula R4R5R6AO, where R4 and R5 are independently selected from hydrogen, C1 to C4 alkyl, or mixtures thereof, and R6 is selected from C12 to C16 alkyl, or mixtures thereof.

In a preferred low-cut amine oxide for use herein, R3 is n-decyl. In another preferred low-cut amine oxide for use herein, R1 and R2 are both methyl. In a particularly preferred low-cut amine oxide for use herein, R1 and R2 are both methyl and R3 is n-decyl.

Preferably, the amine oxide comprises less than 5% by weight of the amine oxide, more preferably less than 3% by weight of amine oxide of the formula R7R8R9AO (wherein R7 and R8 are selected from hydrogen, C1-C4 alkyl, and mixtures thereof, and R9 is selected from C8 alkyl and mixtures thereof). Compositions containing R7R8R9AO tend to be unstable and do not provide strong foam mileage.

Preferably, the zwitterionic surfactant is a betaine surfactant. Suitable betaine surfactants include alkyl betaines, alkylamido betaines, amidoazolinium betaines, sulfobetaines (INCI sultaines) and phosphobetaines, preferably represented by formula (I):
R ¹ -[CO-x(CH ₂ ) _n ] ^x -N ⁺ (R ² )(R ₃ )-(CH ₂ ) _m -[CH(OH)-CH ₂ ] _y -Y- (I)
[In the formula,
R1 is a saturated or unsaturated C6-22 alkyl residue, preferably a C8-18 alkyl residue, in particular a saturated C10-16 alkyl residue, for example a saturated C12-14 alkyl residue;
X is NH, NR4 (with C1-4 alkyl residue R4), O, or S;
n is a number from 1 to 10, preferably from 2 to 5, in particular 3,
x is 0 or 1, preferably 1;
R2 and R3 are independently a C1-4 alkyl residue, which may be hydroxy-substituted, such as hydroxyethyl, preferably methyl;
m is a number from 1 to 4, in particular 1, 2 or 3;
y is 0 or 1;
Y is COO, SO ₃ , OPO(OR5)O or P(O)(OR5)O, and R5 is a hydrogen atom H or a C1-4 alkyl residue.

Preferred betaines are alkylbetaines of formula (Ia), alkylamidopropylbetaines of formula (Ib), sulfobetaines of formula (Ic) and amidosulfobetaines of formula (Id);
R ¹ -N(CH ₃ ) ₂ -CH ₂ COO- (Ia)
R ¹ -CO-NH(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (Ib)
R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ - (Ic)
R ¹ -CO-NH-(CH ₂ ) ₃ -N+(CH ₃ ) ₂ -CH ₂ CH(OH)CH ₂ SO ₃ - (Id)
wherein R1 has the same meaning as in formula (I). Particularly preferred betaines are carbobetaines [wherein Y-=COO-], in particular carbobetaines of formula (Ia) and formula (Ib), more preferably alkylamidobetaines of formula (Ib).

A preferred betaine is, for example, cocoamidopropyl betaine.

Preferably, the surfactant system of the composition of the present invention comprises a surfactant system in which the weight ratio of anionic surfactant to first co-surfactant, preferably the weight ratio of anionic surfactant to amine oxide surfactant, is from 8:1 to 1:1, preferably from 4:1 to 2:1, more preferably from 3.5:1 to 2.5:1.

Nonionic Surfactants Preferably, the surfactant system of the compositions of the present invention further comprises a secondary co-surfactant system in an amount of 0.1% to 10% by weight of the total composition. As used herein, the term "secondary co-surfactant" means the co-surfactant present in the second highest concentration, excluding the primary surfactant, i.e., the anionic surfactant present in the highest concentration, and the amphoteric/zwitterionic/mixture thereof as the primary co-surfactant. Preferably, the secondary co-surfactant system comprises a nonionic surfactant. Preferably, the surfactant system of the compositions of the present invention further comprises from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, and most preferably from 1.5% to 5% by weight of the surfactant system of a nonionic surfactant.

Preferably, the nonionic surfactant is a linear or branched primary or secondary alkyl alkoxylated nonionic surfactant, preferably an alkyl ethoxylated nonionic surfactant, preferably containing an average of 9 to 15, preferably 10 to 14, carbon atoms in the alkyl chain and an average of 5 to 12, preferably 6 to 10, and most preferably 7 to 8, ethylene oxide units per mole of alcohol. Other nonionic surfactants suitable for use herein include fatty alcohol polyglycol ethers, alkyl polyglucosides, and fatty acid glucamides, preferably alkyl polyglucosides. Preferably, the alkyl polyglycoside surfactant is a C8 to C16 alkyl polyglycoside surfactant, preferably a C8 to C14 alkyl polyglycoside surfactant, preferably having an average degree of polymerization of 0.1 to 3, more preferably 0.5 to 2.5, and even more preferably 1 to 2. Most preferably, the alkyl polyglycoside surfactant has an average alkyl carbon chain length of 10 to 16, preferably 10 to 14, most preferably 12 to 14, with an average degree of polymerization of 0.5 to 2.5, preferably 1 to 2, most preferably 1.2 to 1.6. C8 to C16 alkyl polyglucosides are commercially available from several sources (e.g., Simusol® surfactants from Seppic Corporation; and Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP/MB, and Glucopon® 650 EC/MB from BASF Corporation). Preferably, the composition comprises anionic surfactant and nonionic surfactant in a ratio of 2:1 to 50:1, preferably 2:1 to 10:1.

Amphiphilic Polymer Preferably, the composition of the present invention may further comprise from 0.01% to 5%, preferably from 0.2% to 3%, more preferably from 0.3% to 1% by weight of the total composition of an amphiphilic polymer, preferably an amphiphilic alkoxylated polyalkyleneimine, selected from the group consisting of amphiphilic alkoxylated polyalkyleneimines and mixtures thereof.

Preferably, the amphiphilic alkoxylated polyalkyleneimine is an alkoxylated polyethyleneimine polymer comprising a polyethyleneimine backbone having an average molecular weight range of 100 to 5,000 daltons, preferably 400 to 2,000 daltons, more preferably 400 to 1,000 daltons, said alkoxylated polyethyleneimine polymer comprising:
(i) one or two alkoxylation modifications per nitrogen atom with a polyalkoxylene chain having an average of about 1 to about 50 alkoxy moieties per modification, wherein the terminal alkoxy moieties of the alkoxylation modification are capped with hydrogen, C1-C4 alkyl, or a mixture thereof;
(ii) one or two alkoxylation modifications per nitrogen atom with the addition of one C1-C4 alkyl moiety and a polyalkoxylene chain having an average of about 1 to about 50 alkoxy moieties per modification, wherein the terminal alkoxy moiety is capped with hydrogen, C1-C4 alkyl, or a mixture thereof; or (iii) a combination thereof;
The alkoxy moieties include ethoxy (EO) and/or propoxy (PO) and/or butoxy (BO), and when the alkoxylated modification includes EO, it also includes PO or BO.

Preferred amphiphilic alkoxylated polyethyleneimine polymers contain EO and PO groups within the alkoxylated chain, with the PO groups preferably being at the terminal positions of the alkoxylated chain, and the alkoxylated chains preferably being hydrogen-capped.

For example, possible modifications to the terminal nitrogen atom of the polyethyleneimine backbone are shown below, but are not limited to these (where R represents an ethylene spacer, E represents a C1-C4 alkyl moiety, and X- represents a suitable water-soluble counterion):

Also, for example, but not limited to, possible modifications to internal nitrogen atoms in the polyethyleneimine backbone are shown below (where R represents an ethylene spacer, E represents a _C1 - _C4 alkyl moiety, and X- represents a suitable water-soluble counterion):

The alkoxylation modification of the polyethyleneimine backbone consists of replacing hydrogen atoms with a polyalkoxylene chain having an average of about 1 to about 50 alkoxy moieties, preferably about 20 to about 45 alkoxy moieties, and most preferably about 30 to about 45 alkoxy moieties. The alkoxy moieties are selected from ethoxy (EO), propoxy (PO), butoxy (BO), and mixtures thereof. However, alkoxy moieties containing only ethoxy units are outside the scope of the present invention. Preferably, the polyalkoxylene chain is selected from an ethoxy/propoxy block moiety. More preferably, the polyalkoxylene chain is an ethoxy/propoxy block moiety having an average degree of ethoxylation of 3 to 30 and an average degree of propoxylation of 1 to 20, and more preferably an ethoxy/propoxy block moiety having an average degree of ethoxylation of 20 to 30 and an average degree of propoxylation of 10 to 20.

More preferably, the ethoxy/propoxy block moiety has a relative ratio of ethoxy units to propoxy units of 3:1 to 1:1, preferably 2:1 to 1:1. Most preferably, the polyalkoxylene chain is an ethoxy/propoxy block moiety, with the propoxy moiety block being the terminal alkoxy moiety block.

This modification can permanently quaternize the nitrogen atoms of the polyethyleneimine backbone. The degree of permanent quaternization can be 0% to 30% of the nitrogen atoms of the polyethyleneimine backbone. Preferably, less than 30% of the nitrogen atoms of the polyethyleneimine backbone are permanently quaternized. Most preferably, the degree of quaternization is 0%.

Preferred polyethyleneimines have the general structure of formula (II):

The weight average molecular weight of the polyethyleneimine backbone is 600, n in formula (II) is an average of 10, m in formula (II) is an average of 7, and R in formula (II) is selected from hydrogen, _C1 - _C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization of formula (II) may be 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone. The molecular weight of this polyethyleneimine is preferably 10,000 to 15,000.

Another polyethyleneimine has the general structure of formula (II), except that the weight average molecular weight of the polyethyleneimine backbone is 600, n in formula (II) averages 24, m in formula (II) averages 16, and R in formula (II) is selected from hydrogen, _C1 - _C4 alkyl, and mixtures thereof, preferably hydrogen. The degree of permanent quaternization of formula (II) can be 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone. The molecular weight of this polyethyleneimine is preferably 25,000 to 30,000.

The most preferred polyethyleneimine has the general structure of formula (II), where the weight average molecular weight of the polyethyleneimine backbone is 600, n in formula (II) averages 24, m in formula (II) averages 16, and R in formula (II) is hydrogen. The degree of permanent quaternization of formula (II) is 0% of the nitrogen atoms in the polyethyleneimine backbone. The molecular weight of this polyethyleneimine is preferably 25,000 to 30,000, most preferably 28,000.

These polyethyleneimines can be prepared by polymerizing ethyleneimine in the presence of a catalyst, such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, or acetic acid, as described in more detail in WO 2007/135645.

Triblock Copolymers The alkylene oxide triblock copolymers of the present invention are defined as triblock copolymers having alkylene oxide moieties according to formula (I):
(EO)x-(PO)y-(EO)x
(I)
(wherein EO represents ethylene oxide and each x represents the number of EO units in an EO block.) Each x independently averages 1 to 80, preferably 3 to 60, more preferably 5 to 50, and most preferably 5 to 30. Preferably, x is the same for both EO blocks, and by "same" we mean that x varies within a maximum of 2 units, preferably within a maximum of 1 unit, between the two EO blocks, and more preferably both x's are the same number of units. PO represents propylene oxide and y represents the number of PO units in the PO block. Each y averages 1 to 60, preferably 10 to 55, more preferably 10 to 50, and most preferably 15 to 48.

Preferably, the ratio of y to each x in the triblock copolymer is 1:1 to 3:1, preferably 1.5:1 to 2.5:1. Preferably, the average weight percentage of total EO in the triblock copolymer is 30% to 50% by weight of the triblock copolymer. Preferably, the average weight percentage of total PO in the triblock copolymer is 50% to 70% by weight of the triblock copolymer. It is understood that the average total weight percentages of EO and PO in the triblock copolymer add up to 100%. The average molecular weight of the triblock copolymer is 140 to 10,500, preferably 800 to 8,500, more preferably 1,000 to 7,300, even more preferably 1,300 to 5,500, and most preferably 2,000 to 4,800. Average molecular weight is determined using 1H NMR spectroscopy (see Thermo scientific application note No. AN52907), which is an established tool for characterizing polymers, including molecular weight measurement and copolymer composition analysis.

Cyclic Polyamine Preferably, the cleaning composition (100) further comprises a cyclic polyamine. The cyclic polyamine of the present invention is a cleaning polyamine. The cleaning polyamine contains amine functionality that aids in cleaning as part of the cleaning composition (100). The composition of the present invention preferably comprises 0.1% to 10%, more preferably 0.2-5%, especially 0.3% to 2% of the cyclic polyamine by weight of the composition.

As used herein, the term "cyclic amine" encompasses both single amines and mixtures thereof. These amines can undergo protonation depending on the pH of the cleaning medium in which they are used. The cyclic polyamines of the present invention have the following formula (I):

wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are independently selected from the group consisting of NH2, —H, linear or branched alkyl having 1 to 10 carbon atoms, and linear or branched alkenyl having 1 to 10 carbon atoms; n is 0 to 3, preferably n is 1; at least one of R is NH2; and the remaining R are independently selected from the group consisting of NH2, —H, linear or branched alkyl having 1 to 10 carbon atoms, and linear or branched alkenyl having 1 to 10 carbon atoms. Preferably, the cyclic polyamine is a diamine where n is 1, R ₂ is NH2, at least one of R ₁ , R ₃ , R ₄ , and R ₅ is CH3, and the remaining R are H.

The amines of the present invention are cyclic amines having at least two primary amine functional groups. The primary amine may be present in any position within the cyclic amine, but it has been found that, from the perspective of grease cleaning, better performance is obtained when the primary amine is present in the 1,3 positions. It has also been found that cyclic amines in which one of the substituents is -CH3 and the remaining are H provide improved grease cleaning performance. Therefore, the most preferred cyclic polyamines for use in the cleaning composition (100) of the present invention are cyclic polyamines selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, and mixtures thereof.

The compositions of the present invention may contain at least one active agent selected from the group consisting of i) salts, ii) hydrotropes, iii) organic solvents, and mixtures thereof.

Salt The compositions of the present invention may comprise from 0.05% to 2%, preferably from 0.1% to 1.5%, or more preferably from 0.5% to 1% by weight of the total composition of salt, preferably a monovalent inorganic salt, a divalent inorganic salt, or mixtures thereof, more preferably sodium chloride, sodium sulfate, or mixtures thereof, most preferably sodium chloride.

Hydrotrope The compositions of the present invention may comprise from 0.1% to 10%, or preferably from 0.5% to 10%, or more preferably from 1% to 10% by weight of the total composition of a hydrotrope or mixture thereof, preferably sodium cumene sulfonate.

Organic Solvent The composition of the present invention may contain an organic solvent. Suitable organic solvents include C4-14 ethers and diethers, polyols, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic linear or branched alcohols, alkoxylated aliphatic linear or branched alcohols, alkoxylated C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof. Preferably, the organic solvent includes alcohols, glycols, and glycol ethers, or alcohols and glycols. The composition comprises from 0% to less than 50%, preferably from 0.01% to 25%, more preferably from 0.1% to 10%, or most preferably from 0.5% to 5% by weight of the total composition of an organic solvent, preferably alcohol, more preferably ethanol, polyalkylene glycol, more preferably polypropylene glycol, and mixtures thereof.

Adjunct Ingredients The cleaning compositions (100) herein may optionally contain many other adjunct ingredients such as builders (e.g., preferably citrate), chelating agents, conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, structuring agents, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, bleaches and bleach activators, fragrances, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, inorganic cations such as alkaline earth metals such as Ca/Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl, and other mono-, di-, and trivalent salts), and pH adjusters and buffers (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, phosphoric and sulfonic acids, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, borates, silicates, phosphates, imidazoles, etc.).

The elements of the composition of the invention described in relation to the first aspect of the invention also apply mutatis mutandis to the other aspects of the invention.

Inverted Container Assembly The inverted container assembly (10) comprises an inverted container (11) and a liquid dispenser (15) attached to the bottom surface (12) of the inverted container (11).

As shown in Figure 3, the liquid dispenser (11) comprises three basic parts: a body (16), a valve (19) (not shown), and preferably an impact resistance system (23). Preferably, the liquid dispenser (15) does not include a closure lid or seal. Typically, the seal is included for shipping purposes and is removed and discarded after the first use of the cleaning product.

Referring to FIG. 4, the liquid dispenser (15) comprises a body (16). The body (16) comprises a connecting sleeve (17) at its upper end (A) adapted to engage, preferably removably engage, an outer surface adjacent the opening (14) at the bottom of the inverted container (11). Preferably, this arrangement provides a leak-tight contact between the liquid dispenser (15) and the inverted container (11), which helps to prevent leakage.

Alternatively, the connection sleeve (17) may be adapted to engage, preferably removably engage, with an inner surface of the inverted container (11) adjacent the opening (14). In other words, the inverted container (11) is attached to the connection sleeve (17) located horizontally outside the body (16) of the liquid dispenser (15). However, this alternative arrangement is less preferred as there is a higher risk of liquid leakage through the contact between the dispenser (15) and the inverted container (11).

The body (16) may engage, preferably removably engage, with the opening (14) of the inverted container (11) by suitable attachment means commonly known to those skilled in the art, including, by way of non-limiting example, cooperating threads, crimping, clipping means, clasp means, snap-fit means, groove arrangement, bayonet fitting, or permanent welding. Preferably, the external threads on the exterior surface of the opening (14) of the inverted container (11) thread into the internal threads molded on the connecting sleeve (17) (as shown in FIG. 4).

The body (16) includes a central portion (15) axially disposed along the longitudinal axis (L). The connecting sleeve (17) is preferably spaced radially inward toward the central portion (15) and defines an internal exhaust conduit (18). The exhaust conduit (18) functions as a flow path for establishing fluid communication between the liquid contained in the inverted container (11) and the external atmosphere. It will be appreciated that, in use, the connecting sleeve (17) forms a fluid seal between the liquid dispenser (15) and the inverted container (11) so that the cleaning composition (100) contained in the inverted container (11) can enter the liquid dispenser (15) without leakage.

Preferably, the body (16) includes an outer portion (14) at the bottom end (B) adapted to allow the inverted container (11) to rest stably on a flat surface (as shown in FIG. 2). The outer portion (14) may be integrally formed with the body (16). For example, the outer portion (14) may include an annular flange structure (e.g., a skirt) extending axially downward toward the bottom (B) and radially outward, as shown in FIG. 4. While FIG. 4 illustrates the outer portion (14) of the body (16) having a frustoconical shape, this is not necessarily limited to this shape. Other shapes, such as cylindrical, pyramidal, disc-shaped, or multi-legged, may also be used, as long as the inverted container (11) can rest stably on its bottom.

While the body (16) is shown and described herein, it should be understood that there are many variations that may be desirable depending on specific requirements. For example, while the connection sleeve (17) and outer portion (14) are shown as having a uniform material thickness, varying material thickness may be desirable in some applications. As a further example, while some surfaces are described herein as having particular shapes (e.g., frustoconical, flat, etc.), other particular shapes for those surfaces may be desirable depending on the specific application.

Preferably, the liquid dispenser (15) further comprises a valve (19) located on the body (16) that extends across the internal discharge conduit (18). As shown in FIG. 5, the valve (19) has an interior side (20) for contacting the cleaning composition (100) contained within the inverted container (11) and an exterior side (22) for exposure to the external atmosphere (as shown in FIG. 6). The valve (19) defines a dispensing orifice (22) that is openable in response to pressure on the interior side (20) of the valve exceeding pressure on the exterior side (21) of the valve.

Valve (19) is preferably a flexible, elastomeric, resilient, two-way, self-closing slit-type valve mounted within body (16). Valve (19) has a slit (25) defining a dispensing orifice (23). For example, dispensing orifice (23) may be formed from a single slit (25) or two or more intersecting slits (25) that can open to dispense liquid therethrough in response to an increase in pressure within inverted container (11), such as when inverted container (11) is squeezed.

Valve (19) is typically designed to respond to a reduction in the pressure differential across valve (19) by closing dispensing orifice (23) and stopping the flow of liquid therethrough. The amount of pressure required to maintain valve (19) in a closed position depends in part on the internal resistance of valve (19). "Internal resistance" (i.e., cracking pressure) refers to a predetermined resistance threshold to deformation/opening of valve (19). In other words, valve (20) tends not to resist deformation/opening so that it remains closed under the steady-state pressure of liquid bearing against its interior (20). The amount of pressure required to deform/open the valve must overcome this internal resistance. This internal resistance must not be too low, causing liquid leakage, or too high, making dispensing a single dose of liquid difficult. Therefore, the valve (19) preferably has an internal resistance force of the valve (19) that is at least 10 mbar, preferably at least 25 mbar, more preferably less than 250 mbar, even more preferably less than 150 mbar, and most preferably less than 75 mbar. Preferably, the dispensing orifice (23) is designed to be in an open position when there is a pressure difference (Δ) between the inside (20) of the valve relative to the valve on the outside (21) of at least 10 mbar, preferably at least 25 mbar. Preferably, the force exerted on the inside (20) of the valve required to open the dispensing orifice (23) is at least 10 mbar, preferably at least 25 mbar. Preferably, the valve (10) has a surface area of 0.1 cm ² to 10 cm ² , more preferably 0.3 cm ² to 5 cm ² , and most preferably 0.5 cm ² to 2 cm ² . Preferably, the valve (19) has a height of 1 mm to 10 mm, more preferably 2 mm to 5 mm. Other dimensions may be used as long as the dispensing orifice (23) remains in a fully closed position at rest.

As shown in FIG. 5, the valve (19) comprises a flexible central portion (24) having at least one, preferably at least two, and preferably a plurality (i.e., three or more), flat, self-sealing slits (25) extending radially outward toward the distal end (26). It should be understood that a slit valve is intended to refer to any valve having one or more slits in its final functional configuration, including a valve in which one or more slits are fully formed only after the valve is formed and/or installed within the liquid dispenser (1). Each slit (25) preferably terminates just before reaching the distal end (26) of the valve (19). Preferably, the slits (25) are straight (as shown in FIG. 6) or may have a variety of different shapes, sizes, and/or configurations (not shown). Preferably, intersecting slits (25) are equally spaced from one another and are equal in length.

Continuing to refer to FIG. 6, the intersecting slits (25) define four, approximately sector-shaped, equally sized flaps (27) in the valve (19). The flaps (27) can be characterized as openable portions of the valve (19) that change position between a closed rest position (as shown in FIG. 5) and an open position (as shown in FIG. 6) in response to a pressure differential. The valve (19) is designed to be sufficiently flexible to regulate the venting of the external atmosphere. For example, when the valve (19) is closed, if the pressure on the outside of the valve (21) exceeds the pressure on the inside of the valve (20) by a predetermined amount, the closure flaps (27) or openable portions can continue to move inward through a closed position, opening the valve flaps (27) inward. This ability to vent the external atmosphere helps equalize the internal pressure within the inverted container (11) with the pressure of the external atmosphere. It is understood that the valve (19) is designed so that the opening pressure for venting and returning air to the inverted container (11) is low enough to avoid collapse of the inverted container (11) during use. In other words, the resilience (i.e., squeezing force) of the inverted container (11) to return to its original shape after use is greater than the vent opening pressure.

Preferably, the valve (19) does not contact the surface on which the inverted container (11) stands when at rest, nor does it contact the surface being cleaned during dispensing. To date, the valve (19) has been positioned within the body (16), preferably at least 1 mm, more preferably at least 5 mm, and even more preferably at least 1 cm from the resting surface. By positioning the valve (19) above and out of contact with the surface, the risk of capillary leaching through the valve (19) and causing surface contamination and potentially surface damage during storage of the inverted container (11) is reduced.

The valve (19) is preferably molded as a single unit from a flexible, pliable, resilient, and elastic material. Suitable materials include thermosetting polymers, including silicone rubber (available as D.C. 99-595-HC from Dow Corning Corp., USA, or WACKER 3003-40 silicone rubber material from Wacker Silicone Co.), preferably having a hardness ratio of 40 Shore A, linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), LLDPE/LDPE blends, acetate, acetal, ultra-high-molecular weight polyethylene (UHMW), polyester, urethane, ethylene vinyl acetate (EVA), polypropylene, high-density polyethylene, or thermoplastic elastomer (TPE). Valve (19) can also be formed from other materials such as thermoplastic propylene, ethylene, and styrene (including their halogenated counterparts). Suitable valves are commercially available from companies such as APTAR Company, including their SimplySqueeze® valve line.

The valve (19) is normally in a closed position and is capable of withstanding the pressure of the liquid within the inverted container (11) so that the liquid does not leak unless the inverted container (11) is squeezed. Unfortunately, the design of the valve (19) is limited in its effectiveness in preventing liquid leakage from the interior of the inverted container (11) under all circumstances, particularly when the inverted container (11) is subjected to an impact, causing a significant, temporary increase in liquid pressure. Therefore, the applicants have surprisingly discovered that incorporating a baffle (23) and/or an impact-resistant system (23) into the liquid dispenser (15) can help absorb the temporary increase in liquid pressure following an impact and substantially reduce or prevent liquid leakage from the liquid dispenser (15).

Preferably, the liquid dispenser (15) further comprises a baffle (30). Preferably, the baffle (30), if present, is located between the interior (20) of the valve (19) and the shock-resistant system (23) (described below). As shown in FIG. 7, the baffle (30) preferably comprises a blocking member (31) supported by at least one support member (32) that regulates movement of the blocking member (31) between a closed position, blocking liquid flow to at least a portion of the discharge conduit (18), when the baffle (30) is subjected to upstream water hammer pressure. Without being bound by theory, it is believed that the baffle (30) acts as an additional counter force against water hammer, thereby further reducing potential leakage risks. In other words, the baffle (30) functions as a wavebreaker to protect the valve (19) from the turbulent kinetic energy of water hammer. Suitable custom-made baffles (30) are available from the APTAR Group.

Preferably, the liquid dispenser (15) further comprises an anti-shock system (23) (as shown in FIG. 8) located upstream of the valve (19). The anti-shock system (23) comprises a housing (24) having a cavity (25) (not shown) therein. The housing (24) extends longitudinally from the body (16) and radially inward from the sleeve (17). The housing (24) is a substantially rigid structure and may be molded from a plastic material, preferably a thermoplastic material, more preferably polypropylene. As shown in FIG. 8, the housing (31) is substantially cylindrical with a dome toward its upper end (C), preferably having a length along its longitudinal axis (L) of 10 mm to 200 mm, preferably 15 mm to 150 mm, more preferably 20 mm to 100 mm. The cylindrical housing (24) preferably has a diameter of 5 mm to 40 mm, preferably 10 mm to 30 mm. It should be understood, however, that the housing (24) may have any desired size and shape, such as, for example, oval, pyramidal, rectangular, etc. However, the size and shape of the housing (24) will necessarily vary depending on the internal volume required for the compressible material (110). For example, if a larger volume of compressible material (110) is required, a housing with a longer diameter may be preferred. Preferably, the housing (24) has an internal volume of 200 ^mm to 250,000 ^mm , preferably 1,500 ^mm to 75,000 ^mm . Preferably, the compressible material (110) has a volume of 1,000 ^mm to a maximum of 20,000 ^mm , preferably 1,500 ^mm to 15,000 ^mm , and most preferably 2,000 ^mm to a maximum of 10,000 ^mm .

Additionally, the housing (24) includes at least one inlet opening (26a) that provides a fluid flow path for the liquid from the inverted vessel (11) into the housing (24). Preferably, the inlet opening (26a) is an opening between the discharge conduit (18) and the valve (19). The phrase "at least one" inlet opening (26a) refers to one or more inlet openings (26a) located on the housing (24). For example, it may be desirable to have one larger inlet opening (26a) or multiple smaller inlet openings (26a). It is expected that the shear viscosity and density of the liquid contained within the inverted vessel (11) will be taken into consideration when designing the size, shape, and number of the inlet openings (26a). The inlet openings (26a) function as openings to provide a fluid flow path for establishing fluid communication between the liquid contained within the inverted vessel (11) and the housing (24). As shown in FIG. 8, the inlet opening (26a) is preferably located near the bottom of the housing (24) and is preferably rectangular, having a length of 1 mm to 25 mm, preferably 5 mm to 20 mm, and a height of 1 mm to 10 mm, preferably 3 to 7 mm. Alternatively, inlet openings (26a) of other shapes and sizes are also operable, as long as they still provide sufficient liquid flow from the inverted vessel (11) into the housing (24). In another non-limiting example, the housing (24) may have three small, circular inlet openings (26a) spaced equidistantly near the bottom, or one semicircular opening encircling half of the housing (24). Preferably, the inlet openings (26a) have a total surface area of ¹ mm to 250 ^mm , preferably 15 ^mm to 150 ^cm . It is also preferred that the inlet openings (26a) are located toward the bottom of the housing (24).

The housing (24) further comprises at least one outlet opening (26b) that provides a path for the liquid to escape from the housing (24) to the external atmosphere when the dispensing orifice (23) is open.

As shown in FIG. 9, the housing (24) further comprises a cavity (25). The cavity (25) is a hollow, open space within the housing (24). The cavity (25) is adapted to be partially occupied by a compressible material (110). Preferably, the compressible material (110) allows for pressure equalization between the inside of the valve (20) and the outside of the valve (21) and allows/maintains responsive closure of the dispensing orifice (23). In other words, prior to "impact" of the inverted container (11), the compressible material (110) remains uncompressed at a pressure sufficient to keep the valve (19) closed and retain liquid within the inverted container (11). The cavity (25) is also partially occupied by liquid prior to "impact."

Preferably, the compressible material (110) is selected from gas, foam, soft materials such as sponges or balloons, other viscoelastic materials (e.g., polysiloxane), or pistons, preferably gas, more preferably air. Applicants have found that to maintain a closable state responsive to the dispensing orifice (23), the preferred ratio of the volume of gas, preferably air, within the housing (24) at steady state to the volume of the inverted container (11) is greater than 0.001, preferably between 0.005 and 0.05, and more preferably between 0.01 and 0.02. Without wishing to be bound by theory, a minimum compression threshold is believed to be desirable to substantially reduce or prevent the risk of leakage under expected exposure conditions during shipping or use. This minimum compression threshold directly correlates to the volume of liquid that can be stored within the inverted container (11).

It will be apparent that the present invention can be used with any type of inverted container. Preferably, the cleaning product is used with an inverted container (11) of the type shown in FIG. 2. The inverted container (11) may be of any suitable shape or design, as long as it can be placed on a surface without tipping over, within the range described. The inverted container (11) can be made of any flexible plastic material, such as a thermoplastic polymer. The flexible material is sufficiently compressible to deform the inverted container (11), allow for the expulsion of liquid, and yet is sufficiently flexible to allow relatively rapid shape recovery from deformation after expulsion. Preferably, the flexible plastic material is polycarbonate, polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), polyethylene terephthalate (PET), or the like, or a blend or multilayer structure thereof. The flexible plastic material may also include a specific moisture or oxygen barrier layer, such as ethylene vinyl alcohol (EVOH). The flexible plastic material may also partially comprise post-consumer recycled material, such as from bottles or other containers. The inverted container (11) includes an opening (14) (not shown) on its bottom surface to allow liquid to enter the liquid dispenser (1) from the inverted container (2). An opening (12) (not shown) is located on the bottom surface (12) of the inverted container (11). In other words, the inverted container (11) dispenses from the bottom.

Continuing with FIG. 2, the inverted container (11) is preferably a squeezable inverted container (11) having at least one, preferably at least two, elastically deformable sidewalls or sidewalls (3). Preferably, the inverted container (11) is characterized by a deflection of 5 N to 30 N for a 15 mm sidewall, preferably a deflection of 10 N to 25 N for a 15 mm sidewall, and more preferably a deflection of 18 N for a 15 mm sidewall (3). A consumer can grasp the inverted container (2) and squeeze or compress the elastically deformable sidewall (3) to apply pressure (also referred to as "applied force") to force the cleaning composition (100) out of the inverted container (11). As a result, as internal pressure increases, liquid between the inverted container (2) and the valve (19) is dispensed into the external atmosphere through the dispensing orifice (23). When the squeezing or compressive force is removed, the elastically deformable sidewall (3) is released, venting air from the external atmosphere into the cavity (25), decompressing the compressible material (110) within the space (32) and causing the elastically deformable sidewall (3) to return to its original shape. Venting also refills the cavity (25) of the housing (24) with air from the external atmosphere. The vented air returns to the inverted container (11) through the inlet opening (26a) to replenish the volume of the dispensed liquid.

For example, larger-sized inverted vessels (11) can hold larger liquid volumes. When these larger-sized inverted vessels (11) are impacted, a larger mass of liquid is displaced during the water hammer, resulting in a larger transient liquid force (F = m × a - Newton's second law, where "F" is force, "m" is the mass of the displaced liquid, and "a" is the acceleration rate of the displaced liquid), thus creating pressure on the housing (24). Because there is a limit to the transient pressure that can be absorbed by the compressible material (110) per unit volume, once that threshold is exceeded, the remaining transient pressure is transferred onto the valve (19), correspondingly causing leakage. Therefore, a larger volume of compressible material (110) is required when a larger volume of liquid enters the inverted vessel (11) to provide a sufficient shock-resistant buffer to prevent leakage upon eventual water hammer exposure.

Test Methods In order to more fully understand the invention described and claimed herein, the assays described below should be used.

Test Method 1: Leak Resistance Test The purpose of the leak resistance test is to evaluate the ability of a liquid dispenser to prevent leakage of liquid from an inverted container during an "impact." The impact occurs when an inverted container is dropped, liquid dispenser-side down, from a certain height onto a flat surface. The drop is intended to simulate the temporary increase in liquid pressure that occurs with impact in an inverted container. The leak resistance of the liquid dispenser is evaluated through measurement of the volume/weight of liquid leaked when dropped from a specified drop height. A smaller volume/weight of leakage correlates with a better leak resistance of the liquid dispenser. The steps of the method are as follows:
1. A drop test apparatus, as shown in Figure 10, is used. This apparatus consists of two top and bottom open-ended cylindrical tubes with a diameter of approximately 12 cm; i.e., the outer tube (34) tightly surrounds the inner tube (33) which is vertically movable into the outer tube (34), and the outer tube (34) has a cut-out section that allows visual assessment of the relative height of the inner tube (33) within the outer tube (34) by means of a rating scale applied to the outer tube (34). A removable lever (35) is applied to the bottom of the inner tube (33), and an inverted container (2) is positioned within the inner tube (33) with its opening facing downwards so that it rests on the lever. When the lever is manually removed, the inverted container falls, and the amount of leaked liquid after exposure is measured. To do this, a piece of paper is placed on the hard surface at the bottom of the open-ended outer container to capture the leaked liquid. The weight of the paper is measured on a scale before and after the drop test to determine the amount of leaked liquid. The height to which the lever is positioned prior to manual removal is measured as the drop height.

2. An inverted container (2) having a specified volume (e.g., 400 mL) is filled with the liquid dishwashing detergent to be tested to a specified fill level (400 mL) in the inverted container. The liquid fill level, and the type and liquid volume of the inverted container including the dispenser system, are kept constant to allow for comparison of different formulations.

3. As shown in FIG. 4, a liquid dispenser including a valve (Simplicity 21-200 "Simplisqueeze®" valve, available from Aptar Group, Inc.) is assembled with an inverted container (2). The liquid dispenser has a frusto-conical exterior (e.g., a bottom diameter of 65 mm, a top diameter of 34 mm, and a height of 30 mm) for resting on a flat surface, and is optionally equipped with an internally deployed baffle (e.g., a 7 mm diameter with five ribs extending outward from a 4 mm central ball), an anti-shock system (30) according to the present invention, or both. The container to which the liquid dispensing system is connected is a dishwashing detergent container commercially available in the UK in December 2017 from Procter & Gamble Company under the trade name Fairy Original (Dark Green).

4. Set the drop height (2cm to 15cm) on the drop tester.

5. Cut a piece of paper approximately 7 cm x 7 cm to fit the opening at the bottom end of the outer tube (34).

6. Weigh the paper strip using a Mettler Toledo PR1203 balance and record the weight.

7. Place a piece of paper under the opening at the lower end of the outer tube (34).

8. Place the assembled liquid dispenser and inverted container (2) with the liquid dispenser side facing down into the inner tube (33) of the drop tester.

9. With a quick, smooth movement, pull back the lever inside the drop tester.

10. Remove the tube and assembled liquid dispenser and inverted container from the drop tester.

11. Weigh the paper strip again and record the weight. Calculate the difference in paper weight. Delta corresponds to the amount of liquid that leaked from the liquid dispenser.

12. Repeat steps 5 through 11 four more times for a total of five replicates for each test condition.

13. Calculate and report the drop height and average leaked weight per detergent composition.

Test Method 2: Liquid Stringing Resistance Test The purpose of the Liquid Stringing Resistance Test is to evaluate the ability of a liquid detergent composition to prevent/reduce the formation of hair strings at the end of dispensing when finger pressure on an inverted container is released. A HAAKE™ CaBER™ 1 Hair Breaking Elongation Rheometer (Thermo Scientific) is used to evaluate the liquid stringing profile of comparative and exemplary formulations by measuring the time to break the hairs formed when the test sample is extended to a specific strain. The sample diameter is set to 6 mm, the initial sample height is set to 3 mm, the final sample height is set to 17.27 mm, the extension profile is set to linear, and the strike time is set to 100 ms.

Test Method 3: Shear Viscosity Test The shear viscosity of liquid detergent compositions is measured using a DHR-1 rotational rheometer commercially available from TA instrument. Specifically, a cone-plate geometry of 40 mm diameter and 2.008° angle was used, with a truncated head gap of 56 μm. A steady shear was applied to measure shear viscosity at 20° C. over a shear rate range of 0.1 to 1000 1/s, with the shear viscosity at 10 1/s reported.

The following examples are provided to further illustrate the present invention and should not be construed as limiting thereof, as many variations of the present invention are possible without departing from the spirit and scope of the invention.

Example 1: Leakage Resistance Profile The ability of cleaning products comprising a cleaning composition (100) according to the present invention (Inventive Compositions 1 and 2), added to an inverted container comprising a liquid dispenser equipped with a composite silicone valve and baffle system as described in the test method disclosed herein, to substantially reduce or prevent liquid leakage was evaluated and compared to comparative compositions outside the scope of the present invention (Comparative Compositions 1 and 2) and a commercially available formulation (Comparative Composition 3, commercially available in Germany in November 2017 - retailer Lidl's "Geschirr Spul Mittel" Green Tea & Rose dishwashing liquid).

Prepare the above composition by standard mixing of the ingredients listed in Table 1.

The results of the leakage resistance test are summarized in Table 2 below. The results show the amount (g) of liquid composition that leaked as a function of drop height for the inventive and comparative compositions.

These results demonstrate that liquid compositions comprising an anionic surfactant and a first co-surfactant selected from an amphoteric surfactant (Composition 1 of the Invention) or a zwitterionic surfactant (Composition 2 of the Invention) within the specified weight ratio range according to the present invention have greater robustness against water hammer compared to other first co-surfactant systems (Comparative Compositions 1 and 2) or a comparative composition comprising an anionic surfactant and a zwitterionic co-surfactant system outside the weight ratio range according to the present invention (Comparative Composition 3).

Example 2: Liquid Stringing Profile The ability of cleaning products comprising the cleaning composition (100) according to the present invention (Inventive Compositions 1 and 2) to substantially reduce or prevent liquid stringing was evaluated according to the Liquid Stringing Resistance Test Method disclosed herein and compared to comparative compositions outside the scope of the present invention (Comparative Compositions 1 and 2) and a commercially available prior art formulation (Comparative Composition 3, commercially available in Germany in November 2017 - retailer Lidl's "Geschirr Spul Mittel" Green Tea & Rose dishwashing liquid). These formulations were also compared to a formulation of Comparative Composition 3 (Comparative Composition 4) in which the initial product viscosity was reduced from 3,820 mPa·s to 1,045 mPa·s by the single variable addition of 0.2% polypropylene glycol MW 2000. The viscosity reduction of Comparative Composition 4 is measured at 20°C using a Brookfield Model DV-E with a spindle 31 rotation speed of 12 RPM.

The results of the liquid stringing resistance test are summarized in Table 3 below. The results indicate the hair break time (s) of the liquid compositions according to the test protocol described herein.

These results demonstrate that the liquid stringing profile of a liquid detergent composition is primarily determined by the final product viscosity. That is, Comparative Composition 3, which has a higher final product viscosity (i.e., 3,820 mPa·s vs. approximately 1,100 mPa·s) compared to the other inventive and comparative product compositions tested, exhibits a significantly longer hair break time. Therefore, a low product viscosity is desirable to prevent/reduce liquid stringing. Because low product viscosity increases the risk of leakage (static and upon impact), formulating a surfactant system according to the present invention is highly preferred to provide both the desired leakage and stringing reduction/prevention profile.

All parts and ratios herein are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise specified.

Every maximum numerical limitation given throughout this specification should be understood to include every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification should be understood to include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification should be understood to include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

The dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

Claims (30)

A cleaning product comprising an inverted container assembly (10) and a liquid dishwashing cleaning composition (100) contained in the inverted container assembly (10), wherein the inverted container assembly (10) comprises an inverted container (11) having a bottom surface (12) and a top surface (13) positioned away from the bottom surface (12), the bottom surface (12) having an opening (14), and a liquid dispenser (15) attached to the bottom surface (12) of the inverted container (11);
a) the cleaning composition (100) comprises 15% to 40% by weight of the total composition of a surfactant system, the surfactant system comprising:
i) an anionic surfactant selected from the group consisting of sulfate anionic surfactants, sulfonate anionic surfactants, and mixtures thereof;
ii) a first co-surfactant system selected from the group consisting of amine oxide surfactants, betaine surfactants, and mixtures thereof;
the composition comprises the anionic surfactant and the first co-surfactant system in a weight ratio of from 8:1 to 1:1;
A cleaning product, wherein the composition has a shear viscosity of 10 mPa·s to 1,500 mPa·s at 10/s when the shear viscosity is measured at 20°C over a shear rate range of 0.1/s to 1,000/s by a shear viscosity test method using a rotational rheometer having a cone-plate geometry with a diameter of 40 mm and an angle of 2.008° and a truncated head gap of 56 μm, applying steady shear. The cleaning product according to claim 1, wherein the composition has a shear viscosity of 10 mPa·s to 500 mPa·s at 10/s when the shear viscosity is measured at 20°C over a shear rate range of 0.1/s to 1000/s by a shear viscosity test method using a rotational rheometer with a cone-plate geometry having a diameter of 40 mm and an angle of 2.008°, with a truncated head gap of 56 μm, applying steady shear. The cleaning product of claim 1, wherein the weight ratio is between 4:1 and 2:1. A cleaning product according to any one of claims 1 to 3, wherein the surfactant system of the composition further comprises 0.1% to 10% by weight of the total composition of a second co-surfactant system, the second co-surfactant system comprising a nonionic surfactant. The cleaning product of claim 4, wherein the anionic surfactant and the nonionic surfactant are present in a ratio of 2:1 to 50:1. A cleaning product according to claim 4 or 5, wherein the nonionic surfactant is an alkyl ethoxylated surfactant. The cleaning product of claim 6, wherein the alkyl ethoxylated surfactant contains 9 to 15 carbon atoms in the alkyl chain and 5 to 12 units of ethylene oxide per mole of alcohol. The cleaning product according to any one of claims 1 to 7, wherein the first co-surfactant system is an amine oxide surfactant. The cleaning product according to any one of claims 1 to 8, wherein the amine oxide surfactant is selected from the group consisting of linear or branched alkylamine oxides, linear or branched alkylamidopropylamine oxides, and mixtures thereof. A cleaning product according to any one of claims 1 to 9, wherein the composition has a pH in the range of 5 to 12 when measured at a 10% dilution in distilled water at 20°C. The cleaning product according to any one of claims 1 to 10, wherein the composition further comprises 0.1% to 5% by weight of the total composition of an amphiphilic alkoxylated polyalkyleneimine, the amphiphilic alkoxylated polyalkyleneimine being an alkoxylated polyethyleneimine polymer comprising a polyethyleneimine backbone having an average molecular weight range of 100 to 5,000 daltons. A cleaning product according to any one of the preceding claims, wherein the composition further comprises from 0.1% to 10% by weight of the total composition of at least one ethylene oxide (EO)-propylene oxide (PO)-ethylene oxide (EO) triblock copolymer of formula (I):
(EO)x-(PO)y-(EO)x
(I)
(In the formula,
each x independently averages from 1 to 80;
y is, on average, 1 to 60. A cleaning product according to any one of claims 1 to 12, wherein the composition further comprises 0.05% to 2% by weight of salt based on the total composition. The cleaning product of claim 13, wherein the salt is a monovalent, divalent inorganic salt, or a mixture thereof. The cleaning product of claim 14, wherein the salt is sodium chloride. A cleaning product according to any one of claims 1 to 15, wherein the composition further comprises 1% to 10% by weight of the total composition of a hydrotrope. The cleaning product of claim 16, wherein the hydrotrope is sodium cumene sulfonate. A cleaning product according to any one of claims 1 to 17, wherein the composition further comprises 0.01% to 25% by weight of the total composition of an organic solvent. The cleaning product of claim 18, wherein the organic solvent is an alcohol. The cleaning product of claim 19, wherein the alcohol is selected from the group consisting of ethanol, polyalkylene glycols, and mixtures thereof. A cleaning product according to any one of claims 1 to 20, wherein the liquid dispenser (15) comprises a body (16) of the dispenser (15) having a connecting sleeve (17), the connecting sleeve (17) being adaptable to engage an outer surface of the inverted container (11) adjacent the opening (14). 22. The cleaning product of claim 21, wherein the connecting sleeves (17) are radially spaced apart to define internal discharge conduits (18) for establishing fluid communication with the composition contained in the inverted container (11). 2. A cleaning product as described in claim 22, wherein the liquid dispenser (15) comprises a valve (19) extending across the internal discharge conduit (18), the valve (19) having an inner side (20) for contacting the cleaning composition (100) contained within the inverted container (11) and an outer side (21) for exposure to the external atmosphere, the valve (19) defining a dispensing orifice (22) that can be opened in response when pressure on the inner side (20) of the valve exceeds pressure on the outer side (21) of the valve, and the liquid dispenser (15) further comprises a baffle (30) located above the inner side (20) of the valve ( 19 ). 24. The cleaning product of claim 23, wherein the liquid dispenser (15) further comprises an anti-shock system (23) located upstream of the valve (19), and a baffle (30), if present, wherein the anti-shock system (23) comprises a housing (24) having a cavity (25) therein and extending longitudinally from the body (16) and radially inward from the sleeve (17), the housing (24) comprising at least one inlet opening (26a) providing a flow path for the composition from the inverted container (11) into the housing (24), and at least one outlet opening (26b) providing a release path for the composition from the housing ( 24) to the external atmosphere when the dispensing orifice (22) is opened, the cavity (25) adapted to be partially occupied by a compressible material (110). A cleaning product according to any one of claims 1 to 24, wherein the liquid dispenser (15) does not include a closing lid. A cleaning product according to any one of claims 1 to 25, wherein the anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, and mixtures thereof. A cleaning product according to any one of claims 1 to 26, wherein the anionic surfactant has a weight average branching level of 5% to 60%. A method for cleaning tableware using the cleaning product of any one of claims 1 to 27, comprising squeezing the inverted container (11) to dispense the cleaning composition (100) through the opening (14) in the bottom surface (12). Use of a cleaning product according to any one of claims 1 to 27 to reduce or prevent leakage of a cleaning composition (100) from the inverted container (11). Use of the cleaning product of any one of claims 1 to 27 to reduce or prevent stringing of the cleaning composition (100) from the inverted container (11).